Process of separating sulfur from the sulfur-containing constituents of petroleum and making hydrogen carbid.



N0. 793.026. PATENTED JUNE 20, 1905.

H. S. BLAGKMORE.

PROCESS OF SEPARATING SULFUR FROM THE SULFUR CONTAINING OONSTITUENTS 0FPETROLEUM AND MAKING HYDROGEN GARBID. APPLICATION FILED ooma. 1904.

alum" to:

Patented June 20, 1905.

UNITED STATES PATENT OFFICE.

' IIENhY SPENO ER. BLACKMORE, OF MOUNT VERNON, NEIV YORK, ASSIGNOR,

BY DIRECT AND MESNE ASSIGNMENTS, TO BLACK-FORD UTILITY OIL COMPANY, ACORPORATION OF THE DISTRICT OF COLUMBIA.

PROCESS OF SEPARATING SULFUR FROM THE SULFUR-CONTAINING CON STITUENTS OFPETROLEUM AND MAKING HYDROGEN CARBID.

SPECIFICATION forming part of Letters Patent No. 793,026, dated June 20,1905.

Original application filed September '7, 1904, Serial No. 223,625.Divided and this application filed October 29,1904. Serial No. 230,550.

To (1, 11:71 m, it may concern:

Be it known that I, HENRY SPENCER BLACK- Moim, a citizen of the UnitedStates, residing at Mount Vernon, in the county of \Vestchester andState of New York, have invented certain new and useful Improvements inProcesses of Separating Sulfur from the Sulf u r-Containing Constituentsof Petroleum and Making llydrogen Oarbid, of which the following is aspecification, being a division from my appli cation, Serial No.223,625, filed in the United States Patent Office September 7, 190%.

The object of my invention is to separate sulfur from sulfur-containingpetroleum and similar compounds and produce hydrogen carbids in such amanner as to facilitate purification, effect a saving in time and labor,thereby economixing the cost; and it consists in exposing thesulfur-containing petroleum to the action of an alkali-earth-metalcarbid, such as calcium carbid, at a reacting temperature.

In carrying out my invention on a practical basis I proceed as follows,reference being had to the accompanyingdrawings, in which-- Figure 1 isa vertical transverse section through the line a a of Fig. 2, showingretorts partially filled with metal carbid. Fig. 2 is a verticallongitudinal section through the line ;1 1/ of Fig. l; and 3 is a frontview of the purifying apparatus, showing outletpipes.

Similar letters of reference indicate like parts in the various views.

A designates a retort made of any suitable material and provided withthe heads B and B, the said heads being held against the flange of theretort A by means of the screw-clamp O. Through the heads B pass theinlet-pipe I), provided at the inner end with a deflector or spreader v.The retort A is provided at or near the end closed by the head B with asuitable outlet-pipe b controlled by valves I, said pipes communicatingwith a common outlet K. Retorts A are preferably heated by means ofgas-burners L, which are so arranged as to throw the flame dlrectlyunder the retorts, whereby the temperature may be regulated andmaintained uniformly.

In employing the apparatus, as described, in the separation of sulfurfrom sulfur-containing petroleums I fill the retorts A with granulatedcalcium carbid about two inches deep over the entire bottom. I thenclose the retort or receptacle and introduce into and pass through theretort A a current of vaporized sulfur-containing petroleum from theinlet-pipe D, which is thrown upon the surface of the carbid by theextended depending spreader or deliector c. As the sulfur-containingpetroleum passes over the calcium carbid the calcium absorbs the sulfurtherefrom, producing a substance which is practically free from sulfur.The reaction which takes place may be illustrated by the followingchemical formula or equation, which illustrates the action of calciumcarbid on methyl sullid, a hydrocarbon compound containing sulfur,analogous in action to sulfur-containing petroleum:

GeiHeS GREG: 0: "i- CaS,

S+ CR0: 1 CH1;

It will be noted in the foregoing equations that the sulfur is removedfrom the hydrocarbon, forming calcium sullid, while the carbon of thecalcium car-bid unites with a portion of the freed hydrocarbon,producing two molecules of hydrocarbon of less density than the onemolecule of sulfur-containing hydrocarbon acted upon. It is found in thesulfurcontaining petroleums that the heavier products predominate overthe lighter, the reason for which appears to be that the lighterhydrocarbons are condensed by the coupling or joining action of thesulfur combined therewith, upon removal of which by the action of acarbid, such as calcium carbid, the heavier product is transformed intohydrocarbons of lighter or less dense character. This does not appear tobe the case where the sulfur is removed by such agents as. copper oxidor other simple sulfur-extracting or absorbing agents in which thehydrocarbon from which the sulfur is abstracted condenses upon itself,producing products of the heavier hydrocarbon type.

The advantage attained by the employment of a carbid, such as calciumcarbid, will be seen when it is understood that the heaviersulfur-containing hydrocarbon products are transformed by the action ofcarbids, such as calcium carbid, into lighter hydrocarbons, such askerosenes or illuminating-oils, from the otherwise more dense paraffinproducts.

After the sulfur has been abstracted from the sulfur-containing oils orpetroleum products the purified vapor passes out of the retort orreceptacle through the pipes b and the conduit K to a suitablereservoir. (Not shown.)

In starting the reaction it is sometimes advisable to heat the retort orreceptacle by means of the burners L to about 360 Fahrenheit, the draftbeing controlled by the dampers It is found, however, that during thereaction between the sulfur of the sulfur-containing hydrocarbon and thecarbid considerable heat is liberated internally, whereupon afterinducing the reaction by means of the initial heating the burners L maybe shut off and the reaction continued by the heat liberated during thetransformation or purification.

I can use or employ any available sulfurcontaining hydrocarbon orsulfurous petroleum, either in a gaseous or vaporized condition or in apure fluid condition, and I can employ any other alkali-earth-metalcarbid in place of calcium carbid aforesaid, so long as the sulfur ofthe sulfur-containing hydrocarbon or sulfurous petroleum has such anaffinity for the base of the carbid that it is withdrawn or separatedtherefrom when brought in contact therewith.

The term alkali-earth-metal carbid, as employed in this specificationand claims, relates to a compound or union of carbon with analkali-earth metal, be it a normal carbid, acetylid, or other union ofcarbon with the metal or metals aforesaid.

The processes devised in the prior art for the purification from or theremoval of sulfur from sulfurous petroleum or its products have fortheir object the abstraction of the sulfur content with the destructionof the hydrocarbon to which the sulfur is joined without supplying anyavailable ingredient in lieu of the sulfur abstracted, while in myprocess the hydrocarbons left after the abstraction of the sulfurcontent of the sulfurous petroleum.

are augmented or increased in value to the extent of the substitutlon ofthe carbon for the sulfur content removed, therebynot only removing thesulfur with the purification of the petroleum, but simultaneouslyproducing an equivalent of hydrocarbon as a substitute for the sulfureliminated, which hydrocarbon exists in a lighter form and is moreavailable for illuminating purposes.

When the process is employed for the removal of sulfur from sulfurouspetroleum, such as Lima oil, I prefer to first vaporize the oil by theaction of heat and convey this vaporized mixture of hydrocarbon andsulfo-hydrocarbon in contact with the alkaliearth-metal carbid, asaforesaid; but I do not confine myself to this particular method ofprocedure, as the carbid may be introduced in the liquid of liquefiedsulfur-containing hydrocarbon or petroleum, or brought in contacttherewith, or exposed to the action thereof, in any convenient manner.

The term gaseous, as employed herein, is intended to include substancesof vaporous nature or those which may be vaporized by the action ofheat.

My process is not only available for the pnrification of gaseous,vaporous, or vaporized hydrocarbons or sulfo-hydrocarbons, (sulfurouspetroleums,) but is applicable to the purification of the more solidconstituents of the petroleumssuch as parafiin, petrolatum, &c. and 1 donot desire to confine myself to the purification of petroleum as acomposite cornposition, but reserve the right to purify any individualproduct of the sulfur-containing petroleum which may be or may have beenseparated into its individual products by fractional distillation orotherwise prior to separating the sulfur therefrom, whereby theindividual ingredients of the petroleum may be purified separatelyinstead of collectively, as is the case where the petroleum is vaporizedas a whole direct and purified by the abstraction of the sulfur beforeseparation of the individual ingredients.

Having now described myinvention, what I claim as new, and desire tosecure by Letters Patent, is-- 1. The process of removing sulfur frompetroleum containing the same, which consists in exposingsulfur-containing petroleum to the action of an alkali-earth-metalcarbid.

2. The process of removing sulfur from petroleum containing the same,which consists in exposing sulfur-containing petroleum to the action ofcalcium carbid.

3. The process of removing sulfur from the constituents of petroleum,which consists in exposing the sulfur-containing constituent to theaction of an alkali-earth-metal carbid.

4. The process of removing sulfur from the constituents of petroleum,which consists in exposing the sulfur-containing constituent to theaction of calcium carbid.

5. The process of removing sulfur from oil containing the same, whichconsists in exposing the sulfur-containing oil to the action of analkali-earth-metal carbid.

6. The process of removing sulfur from oil containing the same, whichconsists in exposing the sulfur-containing oil to the action of calciumcarbid.

7. The process of producing hydrogen carbid, which consists in exposingan alkaliearth-metal carhicl to the action of sul't'urous petroleum at areacting temperature.

8. The process of producinghydrogen carhid which consists in exposingcalcium carhid to the action of sulfurous petroleum at a reactingtemperature.

9. The process of producing hydrogen carbid which consists in vaporizingsulfurous petroleum and exposing the same to the action of analkali-earth-metal carbid.

10. The process of removing sulfur from sulfurous petroleum, whichconsists in exposing it to the action of an alkali-carth-metal carbid ata reacting temperature.

11. The process of purifying petroleum which consists in exposing thepetroleum to the action of an alkali-earth-metal carbid.

12. The process of purifying petroleum which consists in exposingvaporized petroleum to the action of an alkali-carth-metal carbid.

In testimony whereof I allix my signature in presence of two witnesses.

HENRY SPENCER 1111A CKHOltll.

\Vitnesscs:

H. N. JENKINS, C. C. \Viueu'r.

